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DOI: 10.1055/s-0029-1219577
The First One-Pot Synthesis of Morita-Baylis-Hillman Adducts Starting Directly from Alcohols
Publication History
Publication Date:
10 March 2010 (online)
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Abstract
The first example of one-pot oxidative carbon-carbon bond formation via the Morita-Baylis-Hillman reaction using alcohols is reported. The protocol involves silica gel-DABCO catalyzed oxidation of alcohols to aldehydes with chloramine-T followed by their Morita-Baylis-Hillman reaction with acrylonitrile or methyl acrylate to give 70-87% overall yields of the corresponding Morita-Baylis-Hillman adducts. The present work opens up a new and efficient synthetic route to Morita-Baylis-Hillman adducts directly from alcohols in a one-pot operation.
Key words
oxidation - C-C bond formation - alcohols - chloramine-T - silica gel-DABCO - Morita-Baylis-Hillman adducts
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1a
Morita K.Suzuki Z.Hirose H. Bull. Chem. Soc. Jpn. 1968, 41: 2815 -
1b
Baylis AB, andHillman MED. inventors; Offenlegungsschrift 2155113, 1972; US 3,743,669. ; Chem. Abstr. 1972, 77, 34174 -
1c
Ciganek E. In Organic Reactions Vol. 51: Wiley; New York: 1997. p.201 -
1d
Ghosh AK.Bilcer G.Schiltz G. Synthesis 2001, 2203 -
2a
Basavaiah D.Rao AJ.Satyanarayana T. Chem. Rev. 2003, 103: 811 -
2b
Basavaiah D.Rao KV.Reddy RJ. Chem. Soc. Rev. 2007, 36: 1581 -
2c
Singh V.Batra S. Tetrahedron 2008, 64: 4511 -
3a
Kim JN.Lee KY. Curr. Org. Chem. 2002, 627 -
3b
Wasnaire P.de Merode T.Marko IE. Chem. Commun. 2007, 4755 -
3c
Kim HS.Kim HS.Kim JN. Bull. Korean Chem. Soc. 2007, 28: 1841 -
3d
Cabrera S.Aleman J.Bolze P.Bertelsen S.Jorgensen KA. Angew. Chem. Int. Ed. 2008, 47: 121 -
3e
Ye L.-W.Han X.Sun X.-L.Tang Y. Tetrahedron 2008, 64: 1487 -
3f
Grange RL.Ziogas J.North AJ.Angus JA.Schiesser CH. Bioorg. Med. Chem. Lett. 2008, 18: 1241 -
3g
Cha MJ.Song YS.Han E.-G.Lee K.-J. J. Heterocycl. Chem. 2008, 235 -
3h
Sa MM.Fernandes L.Ferreira M.Bortoluzzi AJ. Tetrahedron Lett. 2008, 49: 1228 -
3i
Yadav LDS.Srivastava VP.Patel R. Tetrahedron Lett. 2009, 50: 1423 -
3j
Yadav LDS.Patel R.Srivastava VP. Tetrahedron Lett. 2009, 50: 1335 -
3k
Reddy CR.Kiranmai N.Johny K.Pendke M.Naresh P. Synthesis 2009, 399 -
3l
Nayak M.Batra S. Eur. J. Org. Chem. 2009, 3505 -
4a
Isaacs NS. Tetrahedron 1991, 47: 8463 -
4b
Rozendaal ELM.Voss BMW.Scheeren HW. Tetrahedron 1993, 49: 6931 -
4c
Roos GHP.Rampersadh P. Synth. Commun. 1993, 23: 1261 -
4d
Bode ML.Kaye PT. J. Chem. Soc., Perkin Trans. 1 1993, 1809 -
4e
Kundu MK.Mukherjee SB.Balu N.Padmakumar R.Bhat SV. Synlett 1994, 444 -
4f
Brzezinski LJ.Rafel S.Leahy JW. Tetrahedron 1997, 53: 16423 -
4g
Brzezinski LJ.Rafel S.Leahy JW. J. Am. Chem. Soc. 1997, 119: 4317 -
4h
Almeida WP.Coelho F. Tetrahedron Lett. 1998, 39: 8609. -
4i
Masunari A.Ishida E.Trazzi G.Almeida WP.Coelho F. Synth. Commun. 2001, 31: 2127 -
4j
Yu C.Liu B.Hu L. J. Org. Chem. 2001, 66: 5413 -
4k
Balan D.Adolfsson H. J. Org. Chem. 2001, 66: 6498 -
4l
Balan D.Adolfsson H. J. Org. Chem. 2002, 67: 2329 -
4m
Aggarwal VK.Dean DK.Mereu A.Williams R. J. Org. Chem. 2002, 67: 510 -
4n
Cai J.Zhou Z.Zhao G.Tang C. Org. Lett. 2002, 4: 4723 -
4o
Chandraekhar S.Narsihmulu Ch.Saritha B.Sultana SS. Tetrahedron Lett. 2004, 45: 5865 -
4p
Mi X.Luo S.Cheng J.-P. J. Org. Chem. 2005, 70: 2338 -
4q
de Souza ROMA.Pereira VLP.Esteves PM.Vasconcellos MLAA. Tetrahedron Lett. 2008, 49: 5902 -
4r
Bugarin A.Connell BT. J. Org. Chem. 2009, 74: 4638 -
5a
Baran PS.Ambhaikar NB.G uerrero CA.Hafensteiner BD.Lin DW.Richter JM. ARKIVOC 2006, (vii): 310 -
5b
Lei M.Hu R.-J.Wang Y.-G. Tetrahedron 2006, 62: 8928 -
5c
Matsuo J.-I.Kawai H.Ishibashi H. Tetrahedron Lett. 2007, 48: 3155 -
5d
Huertu R.Flores-Figueroa A.Ugalde-Saldivar VM.Castillo I. Inorg. Chem. 2007, 46: 9510 -
5e
Clift MD.Taylor CN.Tomson RJ. Org. Lett. 2007, 9: 4667 -
5f
Konkol LC.Jones BT.Thomson RJ. Org. Lett. 2009, 11: 5550 -
6a
Yeo JE.Yang X.Kim HJ.Koo S. Chem. Commun. 2004, 236 -
6b
Krishna PR.Kannan V.Sharma GVM. J. Org. Chem. 2004, 69: 6467 -
7a
Tandon M.Krishna PKZ. Phys. Chem. 1985, 266: 1153 -
7b
Mantzavinos D.Hellenbrand R.Livingston AG.Metcalfs IS. Appl. Catal., B 1996, 11: 99 -
7c
Singh RA.Singh RS. Oxid. Commun. 1997, 20: 248 -
7d
Konyukhov VY.Chernaa IV.Naumov VA. Kinet. Catal. 1997, 38: 811 -
7e
Navarro M.De Giovani WF.Romero JR. J. Mol. Catal. A: Chem. 1998, 135: 249 -
7f
Hirano M.Kojima K.Yakabe S.Morimoto T. J. Chem. Res. Synop. 2001, 274 -
7g
Svetlakov NV.Nikitin VG.Orekhova AO. Russian J. Org. Chem. 2002, 38: 753 -
7h
Joseph JK.Jain SL.Sain B. Eur. J. Org. Chem. 2006, 590 -
7i
Kguchi S.Kitazume T. Tetrahedron Lett. 2006, 47: 2797 -
7j
Jiang N.Ragauskas AJ. Tetrahedron Lett. 2007, 48: 273 - 8
Cainelli G.Cardillo G. Chromium Oxidations in Organic Chemistry Springer; Berlin: 1984. - 9
Harding KE.May LM.Dick KF. J. Org. Chem. 1975, 40: 1664 - 10
Collins JC.Hess WW.Frank FJ. Tetrahedron Lett. 1968, 9: 3363 - 11
Corey EJ.Suggs JW. Tetrahedron 1975, 31: 2647 - 12
Omura K.Swern D. Tetrahedron 1978, 34: 1651 - 13
Annelli PL.Montanari F.Quici S. Org. Synth. 1990, 69: 212 -
14a
Frigerio M.Santagostino M. Tetrahedron Lett. 1994, 35: 8019 -
14b
Frigerio M.Santagostino M.Sputore S.Palmisano G. J. Org. Chem. 1995, 60: 7272 -
14c
De Munari S.Frigerio M.Santagostino M. J. Org. Chem. 1996, 61: 9272 -
14d
Frigerio M.Santagostino M.Sputore S. J. Org. Chem. 1999, 64: 4537 -
15a
Zhdankin VV.Stang PJ. Chem. Rev. 2002, 102: 2523 -
15b
Wirth T. Angew. Chem. Int. Ed. 2005, 44: 3656 -
15c
Ladziata U.Zhdankin VV. ARKIVOC 2006, (ix): 26 -
15d
Zhdankin VV.Stang PJ. Chem. Rev. 2008, 108: 5299 -
16a
Richardson RD.Zayed JM.Altermann S.Smith D.Wirth T. Angew. Chem. Int. Ed. 2007, 46: 6529 -
16b
More JD.Finney NS. Org. Lett. 2002, 4: 3001 -
17a
Banergi KK. Bull. Chem. Soc. Jpn. 1977, 50: 1616 -
17b
Kitagawa H.Mkaiyama T. Chem. Pharm. Bull. 2002, 50: 1276 -
17c
Vinod KN. .Gowda KNN. Inorg. Chim. Acta 2009, 362: 2044 -
18a
Minakata S.Kano D.Oderaotoshi Y.Komatsu M. Angew. Chem. Int. Ed. 2004, 43: 79 -
18b
Minakata S.Hotta T.Oderaotoshi Y.Komatsu M. J. Org. Chem. 2006, 71: 7471 -
19a
Ando T.Kano D.Minakat S.Ryu I.Komatsu M. Tetrahedron 1998, 54: 13485 -
19b
Le Questel JY.Berthelot M.Laurence C. J. Phys. Org. Chem. 2000, 13: 347 -
19c
D’hooghe M.Rottiers M.Kerkaert I.De Kimpe N. Tetrahedron 2005, 61: 8746 -
19d
Minakata S.Hotta T.Oderaostoshi Y.Komatsu M. J. Org. Chem. 2006, 71: 7471 -
19e
Jung Y.Marcus RA. J. Am. Chem. Soc. 2007, 129: 5492 -
19f
Minakata S.Komatsu M. Chem. Rev. 2009, 109: 711 - 20
Witula T.Holmberg K. Langmuir 2005, 21: 3782 -
21a
Yadav LDS.Srivastava VP.Patel R. Tetrahedron Lett. 2008, 49: 3142 -
21b
Yadav LDS.Srivastava VP.Patel R. Tetrahedron Lett. 2008, 49: 5652 -
21c
Yadav LDS.Patel R.Srivastava VP. Synlett 2008, 1789 -
21d
Yadav LDS.Awasthi C. Tetrahedron Lett. 2009, 50: 3801 -
21e
Yadav LDS.Rai VK. Tetrahedron Lett. 2009, 50: 2414 -
21f
Yadav LDS.Rai VK.Singh S. Synlett 2009, 1423 - 23
Gong H.Cai C.-Q.Yang N.-F.Yang L.-W.Ahang J.Fan Q.-H. J. Mol. Catal. A: Chem. 2006, 249: 236
References and Notes
General Procedure
for the Synthesis of MBH Adducts 6
A mixture of alcohol 1 (5 mmol), chloramine-T (2,
5 mmol), DABCO (5 mmol), and SiO2 (200 mg) in 1,4-dioxane-H2O (3
mL, 1:1) was stirred at r.t. until the chloramine-T was consumed
(6-24 h), then acrylonitrile or methyl acrylate (15 mmol)
was added and the mixture was stirred at r.t. for 5-45 h
(Table
[²]
).The reaction
progress was monitored by TLC. Upon completion, the reaction mixture
was evaporated under reduced pressure and extracted with EtOAc (3 × 5 mL).
The combined organic phase was dried over MgSO4, filtered,
and evaporated under reduced pressure. The resulting crude product
was purified by silica gel column chromatography using hexane-EtOAc
as eluent to give pure products 6. The
structure of the products was confirmed by comparison of their mp
or bp, TLC, IR, and NMR data with authentic samples prepared by
literature methods.4j,n,o,q,²³